O-6-hydroxypyridone-2 dyes bearing a cationic group in the 3-position

ABSTRACT

Azo dyes of the formula WHEREIN D is carbocyclic or heterocyclic aryl, R is hydrogen or an organic radical, R1 is hydrogen, hydrocarbyl, heterocyclyl, amino or substituted amino, K is substituted ammonium or hydrazinium (including compounds wherein the nitrogen(s) is (are) part of a heterocyclic ring), and A is an anion. These azo dyes are useful for the dyeing and printing of fibers (and textiles thereof) of acrylonitrile polymers and copolymers as well as polyamides and polyesters containing acidic groups. They give level dyeings having good fastness to light and water.

United States Patent [191 Steinemann 5-ARYLAZO-6-HYDROXYPYRIDONE-2 DYES BEARING A CATIONIC GROUP IN THE 3-POSlTION [75] Inventor: Willy Steinemann, Basel,

Switzerland [73] Assignec: Sandoz Ltd., Basle, Switzerland [21] Appl. No.: 87,602

130] Foreign Application Priority Data Dec. 7, 1969 Switzerland 16561/69 Dec. 23, 1969 Switzerland 19042/69 Aug. 13, 1970 Switzerland 12175/70 Aug. 18. 1970 Switzerland 12339/70 [5 2] US. Cl. 260/156, 8/41 A, 260/146 R, 260/154, 260/155 [51] Int. CL... C09b 29/36, C09b 31/14, D06p 3/76 [58] Field of Search 260/156, 146 R, 154, 155' [56] References Cited UNITED STATES PATENTS 2,431,190 11/1947 Morgan 260/156 X 3,312,681 4/1967 Lewis 260/156 3,487,066 12/1969 Ritter et a1 260/156 FOREIGN PATENTS OR APPLICATIONS 1,901,712 9/1969 Germany 260/156 OTHER PUBLICATIONS Sandoz, Derwent Belgian Patents Report, Number 47/69, pages 2:3 to 2:4 (11-3-1969).

[ 1 Dec. 3, 1974 Primary ExaminerFloyd D. Higel I Attorney, Agent, or FirmGerald D. Sharkin; Richard E. Vila; Melvyn M. Kassenoff [57] ABSTRACT Azo dyes of the formula wherein D is carbocyclic or heterocyclic aryl,

R is hydrogen or an organic radical,

R is hydrogen, hydrocarbyl, heterocyclyl, amino or substituted amino,

K is substituted ammonium or hydrazinium (including compounds wherein the nitrogen(s) is (are) part of a heterocyclic ring), and

A is an anion.

These azo dyes are useful for the dyeing and printing of fibers (and textiles thereof) of acrylonitrile polymers and copolymers as well as polyamides and polyesters containing acidic groups. They give level dyeings having good fastness to light and water.

35 Claims, N0 Drawings -ARYLAZO-6-HYDROXYPYRIDONE-2 DYES BEARING A CATIONIC GROUP IN THE This invention relates to new basic azo dyes free from sulphonic acid groups, which are formed with a dioxypyridine coupling component and in which a cationicnitrogen atom is bound directly on the 3-position of the pyridone. They are highly suitable for the dyeing and printing of polyacrylnitrile and acrylonitrile copolymer fibres and textiles made thereof, including a component of such fibre in blend yarns and fabrics.

These new azo dyes are of the formula m H .9 D-N= N- =o A- N v OH l,

(1)1 where '0 "M M "M v 1 R represents hydrogen or an alkyl, aryl or heterocyclic radical which may be substituted or a carboxwhere ylic acid ester or a carboxylic acid amide radical;

D stands for an aromatic carbocyclic or aromatic het-,

erocyclic radical which may be substituted, and azo dyes the formula R for hydrogen or an organic radical, R, for hydrogen or for a hydrocarbon radical, a heterocyclic radical or anamino group which may be, f f substituted, A for an anion equivalent to the dye cation, D N=N =0 A- and a on K" for a group of the formula 111 (VI),

where R2 R4 R represents an alkyl or aryl radical which may be 1; substituted. (U), 4 A20 dyes of notably good quality correspond to the for- V I m mula Ra -I IR1jl R if) R8 [11 w D =0 A- N OH R2 1 (VII), slam] R3 (IV).

where in formulae (ll), (ill) and (lV) R stands for an alkyl or cycloalkyl radical, which may be substituted, or together with R-;, and the adjacent N atom for a heterocycle,

R for an alkyl or cycloalkyl radical, which may be substituted, or together with R and the adjacent N atom for a heterocycle,

R and R each stands for a hydrogen atom or for identical or different alkyl or cycloalkyl radicals which may be substituted,

R and R each stands for a hydrocarbon radical which may be substituted, R for an alkyl or cycloalkyl radical which may be substituted, 1 5 and where R together with R and/or R together with R and the N atoms adjacent to these substitutents, and/or R and R or R R and R together with the N atom may form heterocycles.

The invention thus comprises azo dyes of the formula D stands for an aromatic carbocyclic or aromatic heterocyclic radical which may be substituted,

R for hydrogen or an organic radical,

R, for hydrogen or a hydrocarbon radical, a heterocyclic radical or an amino group which may be substituted,

A" for an anion equivalent to the dye cation, and- Z for a constituent of a multi-membered ring of aromatic character, for example having five or six members, which may bear further hetero atoms and substituents and on which further rings may be condensed, and, more particularly, to the compounds of the formula (VIIa) wherein D is phenyl, naphthyl, anthraquinonyl, 2-thiazolyl, 2-benzothiazolyl or l,2,4-triazoyl, or a'substituted derivative thereof, wherein each substituent of each substituted derivative is independently lower alkyl, lower 'alkoxy, halo, nitro, cyano, trifluoromethyl, phenyl, lower alkanamidophenyl, phenoxy,

chlorophenoxy, benzyloxy, anilino, nitroanilino,

, dinitroanilino, lower alkanoyl, benzoyl, lower alkylbenzoyl, carbamoyl, dilower alkyl-carbamoyl, phenylcarbamoyl, N-(dilower alkylamino-lower alkyl)carbamoyl, lower alkoxycarbonyl, dilower alkylaminolower alkanoyl, lower alkanamido, di- Iower alkylaminolower alkanamido, lower alkoxycarbonylamino, benzamido, lower alkylsulfonyl, phenylsulfonyl, chlorophenylsulfonyl, benzylsulfonyl, phenoxysulfonyl, sulfamoyl, lower alkylsulfamoyi, dilower alkylsulfamoyl, phenylsulfamoyl, chlorophenylsulfamoyl, N-phenyl-N-low'er alkylsulfamoyL- naphthylsulfamoyl, N-(dilower alkylaminolower alkyl)carbamoyl phenyl, phenylazo, nitrophenylaz'o, chlorophenyla'zo, chlloronitrophenylazo, lower alkylphenylazo, lower alkoxyphenylazo, dilower alkylaminophenylazo, lower alkanamidophenylazo, phenylazophenylazo, phthalimido, 2-oxopyrrolidinyll 2-oxol ,3- oxazolidinyl-l or 6-lower alkylbenzothiaZolyl-Z, and especially phenyl or naphthyl, or a substituted derivative thereof having 1 to 3 substituents, wherein each substituent is independentlylower alkyl, lower alkoxy, chloro, bromo, nitro, cyano, phenyl, 4-acetamidophenyl. phenoxy, 4- chlorophenoxy, benzyloxy, aniline, nitroanilino, 2,4-dinitroanilino, acetyl, benzoyl, 4- methylbenzoyl, carbamoyl, dimethylcarbamoyl, phenylcarbamoyl, .3-(N.N-dimet hylamino)propylcarbamoyi, lower alkoxycarbonyl, acetamido, N,N- dimethylaminoacetamido, lower alkoxycarbonylamino, benzamido, lower alkylsulfonyl, phenylsulfonyl, 4-chlorophenylsulfonyl, benzylsult'onyl. phenoxysulfonyl, lower alkylsulfamoyl, dilower alkyls ulfamoyl, phenylsulfan oyl, 3-chlorop henylsulfam oyl, N-phenyl-N-lower alkylsulfamoyl, naphthylsulfamoyl, phenylazo, nitrophenylazo,

4-chlorophenylazo, tolylazo, lower alkoxyphenylazo, 4-phenylazophe'nylazo, 2- oxbpyrrolidinyll 2-,oxol ,3'-oxazolidinyl-l or phthalirnido, 1

K* is pyridinium, quinolinium, isoquinolinium, quinoxalinium, thiazolium, pyrimidinium,

benzyl, phenyl or dilower alkyl-carbamoyl and especially pyridinium, quinolinium or isoquinolinium, or a substituted derivative thereof, wherein each substituted derivative has 1 to 3 substituents and each substituent of each substituted derivative is independently lower alkyl, methoxy, Z-hydroxyethyl, chloro, bromo, cyano, benzyl or N,N-dimethylcarbamoyl,

R is hydrogen, lower alkyl, monosubstituted lower alkyl, phenyl, furyl, pyridyl', lower alkoxycarbonyl as i; s s

zino, tetrahydrofuryl or dilower alkylamino, or R 'and R taken together and'with the nitrogen to which they are bound are pyrrolidino, piperidino, N'-lower hydroxyalkylpiperazino, hydrazine, N'-lower hydroxyulkylhydrazino or N, N'-dilower hydroxyalkylhydrazino, and

R is especially hydrogen, lower alkyl, phenyl, benzyl,

lower alkoxymethyl, phenoxymethyl, lower alk'oxycarbonyl or O R LN wherein each R is independently hydrogen, alkyl of 1 to 6 carbon atoms, lower hydroxyalkyl, phenyl. o-tolyl or phenyllower alkyl,

R, is hydrogen, alkyl of l to 8 carbon atoms, monosubstituted lower alkyl, phenyl, chlorophenyl. tolyl, N,N-dimethylaminophenyl, anilinophenyl, diphenyl, lower alkylcarbamoyl, amino,dilower alkylamino, lower hydroxyalkylamino, pyrrolidino, morpholino, N-lower alkylpiperazino, pyridyl, tetrahydrofuryl, lower alkylthiazolyl or N-lower alkylpyrrolidinium "A, wherein the substituent of monosubstituted lower alkyl is lower alkoxy, hydroxy, dilower alkylamino, lower hydroxyalkylamino, dilower hydroxyalkylamino, cyano, phenyl, lower alkoxycarbonyl, piperazino, N-lower alkylpiperazino, morpholino, pyridinium *A or N,N- dilower alkyl-hydrazinium A, and especially hydrogen, lower alkyl, lower hydroxyalkyl, methoxylower alkyl, phenyl or phenyllower alkyl, and

A is an anion.

Of the foregoing compounds, those wherein K is pyridinium or substituted pyridinium having 1 or 2 substituents, wherein each substituent is independently methyl or ethyl,

R is hydrogen, lower alkyl or phenyl, and

R is hydrogen, lower alkyl, lower hydroxyalkyl or' where R represents hydrogen, an alkyl, aryl or heterocyclic radical or a carboxylic acid ester or a carbocyclic I acid amide radical and R D, Z and A have the meanings assigned to them in the foregoing;

where R" represents an alkyl or aryl radical which may be substituted and D. R Z and A have the aforestated meanings;

where the pyridinium ring B may be unsubstituted or substituted; and D, R, R and A have the aforestated where V represents R or R" a and D, R B and A" have 'the aforestated meanings;

(XIII) The new azo dyes of formulae (l) and (Vll) can be produced by coupling the diazo compound of an amine of the formula D NH ' (XIV) with a coupling component of the formula Disajzo or polyazo dyes can be produced as desired.

Dyes of the formula (XVII) where R and R each represents a hydrocarbon radical which may be substituted,

R an alkyl or cycloalkyl radical which may be sub-- stituted and where R and R together with the N atom may form a saturated or partially saturated he'terocycle',

can be obtained by quaternization of an azo compound of the formula (XVIII) where R and R each represents a hydrogen atom or a hy-v drocarbon radical which may, be substituted, or which, jointly with the N atom bound thereto, may form a saturated or partially saturated heterocycle.

An alternative method'of producing these new dyes is'to coupleithe diazo compound of an amine of foracetamide chloride, in the presence of a catalyst in a.

solvent, preferably an organic solvent, such as methanol.

The dyes of formula (I) and formula (Hi) can also be produced by the oxidative coupling or coupling of N- nitroso compounds of heterocyclic amines with a compound of formula (XV) or (XVI).

The. new dyes are eminently suitable for dyeing-and printing textiles which consist of polyacrylonitrile or acrylonitrile copolymer fibres .or which contain a component of one of these fibres. They are suitable further for dyeing and printing synthetic polyamide and synthetic polyester fibres modified by the introduction of acid groups. Polyamides of this type are described, for example, in Belgian Patent No. 706,104, while corresponding polyesters are disclosed, e.g. in U.S. Pat. Nos. 3,018,277 and 3,379,723,

The dyes are normally applied from an aqueous medium of neutral or acid reaction at temperatures in the range of 60C to lO0C or at higher temperatures under static pressure. They give level dyeings without the assistance of retar'ders. As stated, they are well suitable for dyeing the polyacrylonitrile or acrylonitrile copolymer fibre component of blend yarns and fabrics.

The dyes of this disclosure which have good solubility in organic solvents are suitable for the coloration of natural materials and natural resins in the 'mass, for the coloration of plastics materials and the dyeing of leather and paper. a

On polyacrylonitrile and acrylonitrile copolymer fibres in particular, but also on other substrates, the dyes produce level dyeings showing good light and wet fastness. Notable features of these dyes are the high tinctorial strength and excellent covering power.

It has been found that mixtures of two or more of the new dyes and mixtures of these with other cationic dyes can be employed advantageously; the dyes are thus suitable for combination dyeing and cause no catalytic fading. The term catalytic fading refers to the type of fading shown by most yellow and greenish to reddish yellow dyes when dyed in combination with-other dyes, in particular blue, violet or red dyes. It is due to interaction between the dyes and is more pronounced than the fading shown-by dyeings of the single dyes.

The dyes of formula (I) give dyeings with good fastness to washing, perspiration, sublimation, pleating, decatizing, pressing, steaming, water, sea water, dry cleaning, cross dyeing and solvents. They are readily soluble, especially in water, show good compatibility with salts, good pH 'stability and withstand prolonged treatment at boiling temperatures. The dyes reserve naturaland synthetic polyamide fibres, provided the latter have notbeen modified by the introduction of acid groups.

it can be assumed that the dyes with a dihydroxypyridone radical are present in a tautomeric'state, which can be represented by the formula l in the dyes, of formula (I) the anion A can be replaced by another. anion, e.g. with the aid of an ion exchanger or by reaction with salts or acids, if necessary in more than one step, for example via the hydroxide or the bicarbonate. The anion A may be an organic or inorganic ion, for example the ion of a halogen, such as chloride, bromide or iodide, or a sulphate, disulphate, methylsulphate, aminosulphonate, perchlorate, carbonate, bicarbonate, phosphate, phosphorus molybdate, phosphorus tungstate', phosphorous tungstic molybdate, arylsulphonate, such as benzenesulphonate, 4-methylbenzenesulphonate, oxalate, maleinate, acetate, propionate, lactate, succinate, chloroacetate, tartrate, methanesulfonate or benzoate ion, or complex anions, such as that of zinc chloride double salts.

The meaning of halogen" may be bromine, fluorine or iodine, but it is preferably chlorine. Examples of organic radicals are hydrocarbon radicals including substituted or unsubstituted alkyl and cycloalkyl radicals, such as cyclohexyl and alkylcyclohexyl radicals, and

substituted or unsubstituted aryl radicals, such as phenyl radicals.

The alkyl radicals may be straight or branched, may be interrupted by hetero atoms and usually bear 1 to 12, l to 6 or preferably 1 to 4 carbon atoms. If these radicals are substituted they contain, in particular, halogen atoms, hydroxyl or cyano groups or aryl radicals, such as phenyl radicals; in such cases alkyl stands for an aralkyl radical, e.g. a benzyl radical. The alkoxy radicals may contain 1 to 6 or preferably 1 to 3 carbon atoms. All the radicals of aromatic character, especially the aromatic carbocyclic and aromatic heterocyclic ones, such as aryl radicals, e.g. phenyl, naphthyl, tetrahydronaphthyl, pyridyl, quinolyl and tetrahydroquinolyl radicals, may bear substitutents, especially non-water-solubilizing substituents, such as halogen atoms, nitro, amino, cyano, thiocyano, hydroxyl, alkyl, alkoxy, trifluoroalkyl, trichloro-alkyl, phenyl, phenoxy, alkylamino, dialkylamino, phenylamino, acyl, acyloxy, acylamino, e.g. acetylamino, benzoylamino, alkylsulphonyl, arylsulphonyl, sulphonic acid amide, sulphonic acid alkylamide, sulphonic acid dialkylamide, sulphonic acid arylamide groups, arylazo,'e.g. phenylazo, diphenylazo, or the COOH group.

The radicals R and R together with the adjacent N atom, may form a heterocycle, e.g. a pyrrolidine, piperazine, morpholine, aziridine or piperidine ring. The radical R jointly with R and/or the R radical jointly with R and the N atoms adjacent to these substituents, may form a saturated or unsaturated, preferably fiveor six-membered heterocycle such as pyrazolidine, pyridazine or pyrazoline ring, e.g. trimethylene pyrazolidine or tetramethylpyrazoline.

The radicals R and R R and R and similarly the radicals R and R or R and R together with the adjacent N atom, may form a saturated or partially saturated heterocycle, for example a pyrrolidine, piperidine, morpholine, aziridine or piperazine ring.

The radicals R R and R together with the adjacent N atom, may form a heterocycle, e.g. a group of the formula or may stand for pyridinium ring.

The heterocyclic radicals R and R and the groups of formula may stand for the radicals of saturated, partly saturated or unsaturated multi-membered rings, preferably fiveor six-membered rings, which may be substituted and on which further cycloaliphatic, heterocyclic or aromatic rings may be condensed. The group of the formula may represent a pyridine, quinoline, isoquinoline, piperidine, pyrrolidine, morpholine, aziridine, piperazine, tetrahydroquinoline, pyrazole. triazole, pyridazine, imidazole, pyrimidine. thiazole, benzothiazole. thiadiazole, indazole. pyrrole. indole, indolenine, oxazole, isoxazole or tetrazole ring, and R may represent a piperidine, pyrrolidine, morpholine. aziridine. piperazine, tetrahydroquinoline, pyridazine, pyrrole or indole ring.

The dyes of formulae (1) and (VII) may bear, in addition to the cationic group K or further cationic groups, e.g., in the radical D and/or in the radical R or R These cationic groups may be hydrazinium, ammonium, cycloimmonium or sulphonium groups. The dyes of these two formulae may also contain protonizable groups, e.g., in the radicals R, and/or R; the term protonizable groups" refers to radicals containing nitrogen which add on a proton in acid, preferably mineral acid medium, to form salts. These are defined in Belgian Patent No. 733,186.

An example of an amino group which may bear substituents is a primary, secondary or tertiary amino group, such as that of the formula where R and R 'each represent hydrogen or a hydrocarbon radical or which, together with the N atom, may form a heterocycle, for example a saturated or partly saturated heterocycle.

Thecarboxylic acid ester radicals may be groups-of the formula --COQX', where X represents a substituted or unsubstituted hydrocarbon radical. The carboxylic acid amide radicals stand primarily for a group of the formula radicals are, as defined, bound directly on the pyridone ring.

Normal methods can be employed for coupling diazotized amines of formula (XIV) with a coupling component of formula (XV) or (XVI), e.g. diazotization with sodium nitrite in hydrochloric acid medium and coupling in aqueous-acid or aqueous-alkaline medium at temperatures of about l0C to room temperature. Quaternatibn can likewise be carried out by known methods, e.g., in an inert solvent, in aqueous suspension with the addition of solvent, or without solvent in an excess of the quaternating agent, if necessary at elevated temperatures and in buffered medium. It is ad vantageous to use organic acids, if necessary in conjunction with a basic compound.

Examples of quaternating agents are alkyl halides such as methyl and ethyl chloride, bromide and iodide, alkylsulphates, such as dimethyl sulphate; benzyl choride; acrylic amides/hydrochloride, e.g. CH =CHCONH /HCI; chloroacetic acid alkylester; Bchloropropionic amide; epoxides, such as ethylene oxide, propylene oxide, epichlorhydrin. The suitable quaternating agents include compounds of formula R A.

The coupling components of formulae (XV) and (XVI) can be produced by reacting a salt of an acetic amide bearing a cationic group, e.g. pyridinium acetamide chloride, with an acylacetic acid ester, e.g. acetoacetic acid methyl ester, in a solvent, preferably organic, such as methanol, and in the presence of a catalyst.

Suitable catalysts are, for example, amines, such a dimethyl amine, diethyl amine, piperidine, morpholine, and ammonium acetate, sodium acetate, potash, so-

' dium carbonate and sodium hydroxide. The dye of the formula imam is disclosed in German published Pat. application 1,040,152 for the dyeing of polyacrylonitrile fibres, on which it gives yellow shades. it is surprising that the dyes of formulae (1) and (V11), which are also of yellow shade, dye polyacrylonitr'ile fibres to considerably greater depth. Both in dye (a) and in the dyes of formulae (l) and (V11) the cationic group is bound directly to a ring. A

The intermediate compounds of formulae (XV) and (XVl) are suitable for varied purposes. They can be employed as optical brighteners and insecticides and as intermediates for the production of optical brighteners and insecticides.

1n the following Examples the parts and percentages are by weightand the temperatures in degrees centigrade.

EXAMPLE 1 9.3 Parts of aminobenzene are diazotized by the normal method in 150 parts of 8 percent hydrochloric acid. A solution'of'25 parts of 2-keto-3-pyridinium chloride-4-methyl-6-hydroxy-1.2-dihydropyridine (prepared by reacting pyridinium chloride acetamide with acetoacetic methyl ester in methanolic sodium hydroxide solution) in 150 parts of water is added dropwise at At the same time I00 parts of a 12.5 percent aqueous sodium acetate solution are added. After completion of coupling. the temperature is increased to 40, hydrochloric acid is added to adjust to a mineral acid reaction. and the new dye. which is present in the form of the chloride, is salted out and filtered. it can be purified by recrystallization. After drying and grinding, it is obtained as a water-soluble powder which dyes polyacrylonitrile and acrylonitrile copolymer fibres in yellow shades of outstanding light fastness.

DYEING METHOD polyacrylonitrile fabric are entered at 60, after pre- 1 treatment for 10-15 minutes at 60 in a bath of 8000 parts of water and 2 parts of glacial acetic acid. The dyebath is raised to in 30 minutes and the fabric dyed for 1 hour at this temperature, with subsequent rinsing. A level yellow dyeing of excellent light and very good wet fastness is obtained.

EXAMPLE 2 14.15 Parts of l-amino-3-chloro-4-methy1benzene are diazotized with 6.9 parts of sodium nitrite. A solution of 25 parts of 2-keto-3-pyridinium chloride-4- methyl-6-hydroxy-l,2-dihydropyridine (prepared by reacting pyridinium chloride acetamide with acetoacetic methyl ester in iso-propanolic sodium hydroxide solution) in 200 parts of water is dropped into the icecold diazo solution. 15 Parts of crystallized sodium acetate'are gradually added to the coupling solution. Stirring is continued at 0-20 and then at 40, with the addition of hydrochloric acid to obtain a mineral acid reaction. The new dye is salted out by adding common salt and purified by recrystallization. A yellow watersoluble powder is obtained which gives level, fast-tolight yellow dyeings on polyacrylonitrile fibres.

Dyes of comparably good quality are obtained when the 14.15 parts of 1-amino-3-chloro-4-methylbenzene employed in the foregoing Example are replaced by an equivalent amount of one of the following amines and the procedure of this Example followed:

l-aminobenzene 1-amino-2-chlorobenzen'e l-amino-3-chlorobenzene l-amino-2 ,6-dichlorobenzene 1ramino-2,3-dichlorobenzene l-amino-2 ,S-dichlorobenzene l-amino-2 ,4-dichlorobenzene l-amino-3 ,4-dichlorobenzene 1 -amino-3 ,S-dichlorobenzene l -amino-4-acetaminobenzene 1-amino-2-ch1oro-4-acetaminobenzene l-amino-4-benzoylaminobenzene 1-amino-4-phenylbenzene 4-amino-l ,1 -diphenylether v 4-amino-4-chloro-l ,1 -diphenylether 2-amino-4'-chloro-l ,1 -diphenylether 2-amino-1 1"-diphenylether 1-amino-2-chloro-4-methylsulphonylbenzene l-amino-4-methylsulphonylbenzene 1-aminobenzene-3-sulphonic acid phenylester 1-amin0benzene-4-sulphonic acid phenylester l-amino-2-chlorobenzene-5-sulphonic acid phenylester acid I 1-amino-2-(trifluoromethyl)-4-chlorobenzene l-amino-4-carbethoxyaminobenzene 1-amino-2 ,5 -dimethoxy-4-carbethoxyaminobenzene l-aminonaphthalene l-aminonaphthalene-4-suiphonic acid dimethyiamide 4-aminophenyl-phthalimide 2-aminoterephthalic acid-dimethylester 4-aminobenzophenone 4-amino-4-methylbenzophen0ne l-amino-4-acetylbenzene 4-amino-2 ',4 '-dinitrodiphenylamine 4-amino-4'-nitrodiphenylamine 4-amino-2'-nitrodiphenylamine- Z-aminothiazole 2- amino-5-methoxybenzothiazoie l-amino-Z-methylbenzene l-amino-3-methyibenzene l-amino-4-methylbenzene 1-amin0-2,5-dimethylbenzene 1-amin0-2-methyi-3 chlorobenzene 1-amino-2-methyl-6-chlorobenzene .l-amin-Z-methyl-S-chlorobenzene I-amino-2-chioro-4-methylbenzenel-aminc-3-chloro-4-methyibenzene l-amin0-3;6-dichIore-4-methylsuifamoylbenzene l-amino-2-chl0ro-4-nitrobenzene l-amin0-2-bromo-4-nitrobenzene l-amin0-2,5-dichioro-4-methoxybenzene l-amino-Z-methoxybenzene l-amino-4-methoxyben'zene I -amin0-2,S-dimethylbenzene l'-amino-2-methyi-3-chlor0benzene l-amin0-2-methyl-6-chlorobenzene l-amino-2-methyl-5-chlorobenzene l-amino-2-chioro-4-methylbenzene l-amino-3-chloro-4-methyibenzene i-amino-3,6-dichloro-4 dimethylsufamoylbenzene l-aminc-2-chioro-4-nitrobenzne i-amin0-2-br0mo-4-nitrobenzene l-amin0-2 ,5-dichloro-4-methoxybenzene l-amino-Z-methoxybenzene l-amino-4-methoxybenzene l-amin -3-chioro-4-methoxybenzene l-amino-Z-ethoxybenzene l-amino-4-ethdxybenzene l-amino-4-benzoxybenzene l-aminophenylacetamide i-aminophenyiacetanilide l-amino-Z-cyanobenzene l-amin0-4-cyanbbenzene l-amino-S-cyanobenzene l-aminc-2-cyano-4-nitrobenzene l amin0-2-cyano-4-nitro--bromobenzene i-amino- 2-nitro-4-methylbenzene l-amino-2-nitro-4-chlor0bcnzene l-aminc-.2;5-dimeth0xy-4-chlorobenzene l-amin0-2,5-dimethoxy-4-bromobenzene l-amino2 ,5 dimethoxybenzene l-amino-2 ,S-diethoxybenzene l-amino-2,S-dimethoxy-4-acetaminobenzene 14 l--amin0-2,5-dimethoxy-4-benzoylaminobenzene l-amino-2,5-diethoxy-4-benzoyiaminobenzene l-aminobenzene-'4-sulphonic acid niethylamide 1-aminobenzene-4 sulphonic acid dimethyiamide 1-aminobenzene-4-sulphonic acid phenylamide l-aminobenzene-4-sulphonic acid -2 chlorophenylamide l-aminobenzene-3-sulphonic acid phenylamide l-aminobenzene-2-sulphonic acid-N- ethylphenylamide l-aminobenzene-2-methyl-5-sulphonamide l-amino-4 methyibenzene-3-sulphonic acid N- ethylphenylamide v l-amino-4-methylbenzene-3-sulphonic acid phenylamide l-amino-2,5-dichlorobenzene 4-suiphonic acid phenylamide l-amino-3-nitrobenzene l-amino-4-nitrobenzene l-amino-2-meth xy-4-nitrobenzene l-amin0-2,5-dimethoxy-4-nitrobenzene l-amino-2,S-dinitrobenzene 1-aminobenzene-4-carboxylic acid methylester 1-aminobenzene-4-carboxylic acid ethylester l-amino-2-methylbenzene-4-carboxyiic acid ethylester i-amino-2-methylbenzene-4-carboxylic V phenylamide 1 amin0benzene-4-carboxyiic acid phenylamide l-aminobenzene-4-carboxylic acid dimethylamide l-aminobenzene-4 carboxylic acid amide l-aminobenzene-Z-caiboxylic acid amide acid i-amino-4-chlorobenzene-Z-Carboxylic acid methylester v l-aminobenzene-2-carboxylic acid methyiester l aminobenzene-3-carb0xylic acid methylester l-aminobenzene-3 carboxylic acid phenylamide l-amino-3-nitro-4-methylbenzene l-amino-2-nitro-4-methoxybenzene 2-aminobenzothiaz0le-6-sulphonamide 2-aminoanthraquin0ne 4-aminoazobenzene i 1-amin0-3-acetaminobenzene l-aminobenzene-4-sulphonic 'acid naphthyl-(1) amide 2-(4'-amino)-phenyi-6-methylbenzothiazole 3-amino-l ,2,4 triazoie I-amin0-2-nitro-4-methylbenzene 1-amin0-2,4,6-trichldrobenzene l-amino 4-( w-dimethylamino )-acetylbenzene 1-amin -2-nitro-4-acetaminobenzene 4-amino-2-methyi-5-methoxyazobenzene 4-amin0-2,5-dimethoxyazobenzene 4-amino-4'-nitroazobenzene 4-amino-4'-acetaminoazobenzene 4-amino-4'-dimethylaminoazobenzene l-amino-4'-phenylaz0naphthalene l-amino-2-ethoxy-4 -phenyiazonaphthalene 4-amino-3'-methylazobenzene 4-amino-4' methoxyazobenzene EXAMPLE 3 i4.i5 Parts of l-amino-2-methyl-3-chlorobenzene are diazotized in the known way with 6.9 parts of sodihydropyridine,

quinolinium methyl pyridiniurn chloride acetic acid methyl amide in ethanol in the presence of potassium hydroxide) are ample 2, Other equally good dyes result whenthe 28 parts of l,2,4-trimethyl-2-keto-3-pyridinium chloride- 6-hydroxyl.2-dihydropyridine used in this Example are replaced by the equivalent amount of l-(3"- methoxy)-n-propyl-2-keto-3-(2'fchloi'oypyridinium chloride-4 methyl-6'-hydroxyl ,Z-dihydropyridine, l-nbutyl-2-keto-3-(4-ethyl)-pyridinium chloride-4- v methyl-o-hydroxy-l ,Z-dihydropyridine, l-(Z "-ethyl)- hexyl-2-keto-3-( 3 '-cyano)-pyridiniu'm chloride-4- rnethyl-6-hydroxyl ,2-dihydropyridine, l-(2 hydroxy)-ethyl-2-keto-3-(2"'-methoxy)-pyridinium chloride-4-methyl-6-hydroxyl ,2-dihydropyridine, l-( 2 N"-methylpiperazinyl-ethyl-2sketo-3-(2-methyl)- pyridinium chloride-4-carbethoxy-6-hydroxy-l,2- l-( 2'f-hydroxyethylamino)-ethyl-2- keto-3-( 3 '-methyl )-pyridinium chloride-4-methyl-6- hydroxy-l,Z-dihydropyridine.

The uforenamed coupling components can also be employed in the procedures of Examples i. 2.4. 5 and 12.] Parts of lamino-2.S-dimethylbenzene are diazotized by the known method with'6.9-parts of sodium nitrite. 42 parts of l-(2"-ethyll-hexyl-2-keto-3- chloride-4-methyl--hydroxyl .2- dihydropyridine (prepared by condensation of acetoacetic ester with quinolinium chloride acetic acid-2- ethylhexyla'mide in iso-propanol by means of magnesium oxide) are dissolved in 200 parts'of water and the solution added dropwise to the ice-cold diazosolution. Sodium acetate is then added and the reaction solution raised to 45. The dye formed is precipitated by the addition of sodium chloride and purified by recrystallization. A yellow water-soluble powder is obtained which dyes polyacrylonitrile and acrylonitrile copolymer fibres in fast yellow shades.

Dyes of equally good quality are obtained when the 12.! putts of l-amino-2.5-dimethylbenzene used in the A foregoing Example are replaced by an equivalent amount of one of the amines named after Example 2. using the procedure of Example 4. Other valuable dyes can be produced by the same procedure using. in place of the 42 parts of quinolinium chioride-4-methyl-6 hydroxyh l ,2=' dihydropyridine, the equivalent amount of l-methyl=2- kcto-Il-isoquinolinium chloride-4-methyl--hydroxy i,2-dihydropyridine. These coupling components can also be employed in the other Examples.

EXAMPLE 5 l2.3 Parts of l-amlno=4-methoatybenzene are diazo= tized by the normal method with 6.9 parts ofsodium nitrite. 33 Parts of l-phenyl-24ceto-3-pyridlnlurn ClllOIe' 'methyl-6-hydroxy-l ,Z-dihydropyridine 16 ide-4-methyl-6-hydroxy-l ,Z-dihydropyridine (prepared by condensation of pyridinium chloride acetic anilide with acetoacetic ester in ethanol and sodium hydroxide) are dissolved in 200 parts of water and the solution dropped into the ice-cold diazo solution. Sodium acetate is gradually added with stirring 'at 05, stirring being continued to completion of the reaction. The temperature .is increased to and the dye precipitated from solution with sodium chloride. it is obtained as a watensoluble powder which gives level yellow dyeings on polyacrylonitrile fibres.

Dyes of comparable quality can beproduced by the procedure of the foregoing Example with the 12.3 parts of l-amino- -l-methoxybenzene replaced by an equivalent amount of one of the amines listed after Example 2. Other equally good dyes are obtainable by the same procedure using, in place of the 33 parts of l-phenyl-Z- keto-3-pyridinium chloride-4-methyl-6-hydroxy-l,2- dihydropyridine, the equivalent amount of l-(2"- chloro)-phenyl-2-keto-'3-pyridinium chloride-4- or l-(3"- methyl )-phenyl-2-keto-3-( 2 '-methyl )-pyridinium chloride-4-methyl-6-hydroxyl ,Z-dihydropyridine. The aforenamed coupling components can also be employed in Examples 1 to 4 and 6.

EXAMPLE 6 12.75 Parts of l-amino-Z-chlorobenzene are diazotized with 6.9 parts of sodium nitrite. 30 Parts of ldimethylamino-2-keto-B-pyridinium chloride-4- methyl-o-hydroxy-l,2-dihydropyridine (prepared by condensation of pyridinium chloride acetic acid-N',N'- dimethyl hydrazide with acetoacetic ester in the presence of magnesium oxide) are dissolved in 200 parts of water and the solution dropped into the ice-cold diazo solution. At the same time an aqueous sodium acetate solution is dropped in. After the coupling reaction is complete, the dye formed is precipitated from solution with sodium chloride in the form of yellow watersoluble crystals. it gives fast yellow dyeings on polyacrylonitrile fibres.

Comparably good dyes can be produced by the procedure of this Example by replacing the 12.75 parts of l-amino-2-chlororobenzene by the equivalent amount of one of the amines named after Example 2. Other equally good dyes are obtainable by this procedure using,'in place of the 30 parts of l-climethylamino-Z-keto- S-pyridinlum chloride-4-methyl-6*hydroxy l ,2- dihydropyridine an equivalent amount of l-amino-2 ketQ-B-pyridinium chloride-4-methyl-6-hydroxy-l ,2- dihydropyridine. l-pyrrolidinyl-2-keto-3-pyriclinium chloride-4methyl-6-hydroxy-l .IZ-dihydropyridine. l-

(N-methyl)-plperazinyl-2-keto-3-pyridinium chloride 4-methyl-6-hydroxyl ,Z-dihyropyridine.

1- morpholinyl-2-keto=3=pyridinium chlorlde4=methyl-6- hydroxy-l .2-dihydropyrldine, l-(4'-dimethylumino) phenyl-2-keto-3-( 2 methyl l-pyridinium chloride-4 methyl-6 hydroxyl ,2-dihydropyridine, "Lamina-2- keto-3-pyridinium chlorlde-l-carbethoxy=6-hydroxyl .Z dlhydropyridine, l dlmethylamino-ketoll pyridiniurn chloride-4 phenyl hydroxy -i .2 dihydropyrldine, M 3 =dirnethylamino lm=propyi=2= dihydropyridine 1-(2 '-dihydroxyethylamino)-ethyl-2- keto-3-pyridinium chloride-4-methyl-6-hydroxy-1,2-

The aforenamed coupling components can be employed in the other Examples.

EXAMPLE 7 21.9 Parts of 3-aminobenzoic acid-3'-dimethylamino-n-propylamide are diazotized at An icecold aqueous hydrochloric acid solution of parts of 3-pyridinium chloride-2,6-di-hydroxy-4- methylpyridine is added to the hydrochloric acid diazo solution. The pH of the reaction solution is adjusted to 2.5 by dropping in 50 percent aqueous sodium acetate solution. After formation of the dye it is salted out with sodium chloride and collected on a filter. The dye is a yellow water-soluble powder which gives greenish yellow dyeings of good light and wet fastness on polyacrylonitrile fibres.

EXAMPLE 7a A solution of 14.15 parts of l-amino-3-chloro-4- methylbenzene in 200 parts of 6 percent hydrochloric acid is diazotized at 0 with 6.9 parts of sodium nitrite. 31 Parts of 2-keto-3-pyridinium chloride-4-carbethoxy- 6-hydroxy-l,Z-dihydropyridine (prepared by reacting pyridinium chloride acetamide with oxalacetic diethyl ester in methanolic sodium hydroxide solution) are dissolved in 200 parts of water and the solution added dropwise to the ice-cold diazo solution. Finally, 15 parts of crystallized sodium acetate are added. The coupling solution is stirred at 020, whereupon the temperature increases to Hydrochloric acid is added to adjust to a mineral acid reaction, then the dye formed is salted out with sodium chloride and collected on a filter. The resulting yellow water-soluble powder has the formula mogooo N and dyes polyacrylonitrile fibres in fast yellow shades.

1.8 EXAMPLE 7! A solution of 14.15 parts of l-amino-3-chloro 4- methylbenzene in 200 parts of 6 percent hydrochloric acid is diazotized at 0 with 6.9 parts of sodium nitrite. 3| parts of 2-keto-3-pyridinium chloride-4-N,N- dimethylcarbamoyl--hydroxyl ,2-dihyd ropyridine (prepared by reacting Z-ketO-B- yridinium chloride-4- carbethoxy-o-hydroxy-l,Z-dihydropyridine with dimethylamin e) are dissolved in 200 parts of water and the solution added dropwise to the ice-cold diazo solution. After the addition of 15 parts of crystallized sodium acetate the coupling solution is stirred at 020, then the temperature is increased to 40. Hydrochloric acid is added to ajust to a mineral acid reaction and the dye formed salted out with sodium chloride and collected on a filter. It is a yellow water-soluble powder of the formula which dyes polyacrylonitrile fibres in fast yellow dsha z r The structures of further dyes are shown in the following table. They can be produced as described in the foregoing Examples and correspond to the formula where D, R, and ,K have the meanings assigned to them in the table. The anion A may be any of .those named in the disclosure.

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1. A COMPOUND OF THE FORMULA
 2. A compound according to claim 1 wherein D is phenyl or naphthyl, or a substituted derivative thereof having 1 to 3 substituents, wherein each substituent is independently lower alkyl, lower alkoxy, chloro, bromo, nitro, cyano, phenyl, 4-acetamidophenyl, phenoxy, 4-chlorophenoxy, benzyloxy, anilino, nitroanilino, 2,4-dinitroanilino acetyl, benzoyl, 4-methylbenzoyl, carbamoyl, dimethylcarbamoyl, phenylcarbamoyl, 3-(N,N-dimethylamino)propylcarbamoyl, lower alkoxycarbonyl, acetamido, N,N-dimethylaminoacetamido, lower alkoxycarbonylamino, benzamido, lower alkylsulfonyl, phenylsulfonyl, 4-chlorophenylsulfonyl, benzylsulfonyl, phenoxysulfonyl, lower alkylsulfamoyl, dilower alkylsulfamoyl, phenylsulfamoyl, 3-chlorophenylsulfamoyl, N-phenyl-N-lower alkylsulfamoyl, naphthylsulfamoyl, phenylazo, nitrophenylazo, 4-chlorophenylazo, tolylazo, lower alkoxyphenylazo, 4-phenylazophenylazo, 2-oxopyrrolidinyl-1, 2-oxo-1,3-oxazolidinyl-1 or phthalimido, K is pyridinium, quinolinium or isoquinolinium, or a substituted derivative thereof, wherein each substituted derivative has 1 to 3 substituents and each substituent of each substituted derivative is independently lower alkyl, methoxy, 2-hydroxyethyl, chloro, bromo, cyano, benzyl or N,N-dimethylcarbamoyl, R is hydrogen, lower alkyl, phenyl, benzyl, lower alkoxymethyl, phenoxymethyl, lower alkoxycarbonyl or
 3. A compound according to claim 2 wherein K is pyridinium or substituted pyridinium having 1 or 2 substituents wherein each substituent is independently methyl or ethyl, R is hydrogen, lower alkyl or phenyl, and R1 is hydrogen, lower alkyl, lower hydroxyalkyl or 3-methoxypropyl.
 4. A compound according to claim 3 wherein D is phenyl or substituted phenyl having 1 to 3 substituents, wherein each substituent is independently methyl, methoxy, chloro, nitro, phenoxy, 4-chlorophenoxy, phenyl or phenylazo, K is pyridinium, methylpyridinium or dimethylpyridinium, R is methyl or phenyl, R1 is hydrogen, methyl, 1-hydroxypropyl-2, 2-hydroxyethyl or 3-methoxypropyl, and A is Cl .
 5. A compound according to claim 1 wherein K is pyridinium.
 6. The compound according to claim 4 having the formula
 7. The compound according to claim 4 having the formula
 8. The compound according to claim 4 having the formula
 9. The compound according to claim 4 having the formula
 10. The compound according to claim 4 having the formula
 11. The compound according to claim 4 having the formula
 12. The compound according to claim 4 having the formula
 13. The compound according to claim 4 having the formula
 14. The compound according to claim 4 having the formula
 15. The compound according to claim 4 having the formula
 16. The compound according to claim 4 having the formula
 17. The compound according to claim 4 having the formula
 18. The compound according to claim 4 having the formula
 19. The compound according to claim 4 having the formula
 20. The compound according to claim 4 having the formula
 21. The compound according to claim 4 having the formula
 22. The compound according to claim 4 having the formula
 23. The compound according to claim 4 having the formula
 24. The compound according to claim 4 having the formula
 25. The compound according to claim 4 having the formula
 26. The compound according to claim 4 having the formula
 27. The compound according to claim 4 having the formula
 28. The compound according to claim 4 having the formula
 29. The compound according to claim 4 having the formula
 30. The compound according to claim 4 having the formula
 31. The compound according to claim 4 having the formula
 32. The compound according to claim 4 having the formula
 33. The compound according to claim 4 having the formula
 34. The compound according to claim 4 having the formula
 35. The compound according to claim 4 having the formula 